Substituted gluconamides



Patented Feb. 23, 1954 V UNITED STATES on-"lcc SUBSTITUTED GLUCONAMIDES No Drawing. Application April 5, 1949, Serial No. 85,711

(Granted under Title 35, U. S. Code (1952),

see. 266) '7 Claims.

This application is made under the act of March 3, 1883, as amended by the act of April 30, 1928, and the invention herein described, if patented in any country, may be manufactured and used by or for the Government of the United States of America for governmental purposes throughout the world without the payment to us of any royalty thereon.

This invention relates to a new class of chemical compounds useful as wetting agents and textile assistants. More particularly, the invention relates to the preparation of a new class of sulfuric acid derivatives of substituted gluconamides and their corresponding alkali metal salts.

The compounds of this invention especially in the form of their alkali metal salts are water soluble and possess the advantageous property of reducing the surface tension of water and other aqueous solutions to a remarkable degree.

The substituted gluconamides employed. in our invention may be represented by the following general formula: RNHCO CHH 4CH2OH in which the radical R is a saturated or unsaturated straight or branch chain aliphatic hydrocarbon radical of from eight to eighteen carbon atoms and in which R may also be a rosin residue. They may be prepared by reaction between D-gluconolactone and the requisite primary amine.

The primary amines include straight and branch-chain aliphatic, either saturated or unsaturated. They also include the so-called rosin amines, such as dehydroabietylamine,

CH3 (1H3 (3H C H:

dihydroabietylamine, tetrahydroabietylamine,

dextropimarylamine, and the like. Mixtures of these or the individual constituents may be employed. in the specific examples given below, the rosin amine employed was a commercial product, Rosin Amine D, having a molecular- The corresponding alkali metal salts of these compounds are simply obtained by neutralization of the sulfuric esters with an alkali metal base. The number of hydroxyl groups so transformed may vary from one to three or more,

4 depending upon the molecular ratio of sulfating agent employed. The following specific examples illustrate the invention.

EXAMPLE 1 Preparation of N-2-ethylhemyZ-D-gluconamide A solution was prepared consisting of 23.2 g. of 2-ethylhexylamine in 250 ml. of methanol. This solution was placed on a steam bath and 32' g. of D-gluconolactone was added portion-wise over a 15-minute period. The mixture was re-:

fluxed for 15 minutes and then cooled. The

white product which crystallized was removed.

by filtration, washed with cold ethanol and dried at C. A first crop of 27.9 g. was obtained, M. P. 116-118 C. Two more crops totalling 24.6 g. were isolated from the mother liquor, giving a total yield of crude product of percent of.

theory.

After recrystallization from ethanol the N-2- ethylhexyl-D-gluconamide melted at 117-118 C.

Analysis.Calcd. for: C14H29OeN: N, 4.5 percent. Found: N, 4.5 percent.

gluconamide sulfuric ester was recovered as in the above Example 8, dissolved in 150 ml. of water and neutralized to pH 7.1 with sodium hydroxide solution. The neutral solution was con- In a similar manner additional substituted 5 eentrated in vacuo to a White produ t Weighing gluconamides were prepared. The data obtained (t eo y 6-2 8.) are summarized in the following table. AnaZZ/ -Ca1 -I S. 9.1. Found: N,

In Example 8, above, the substituted glucon- TABLE I 10 amide was reacted with a molecular equivalent of chlorosulfonic acid, whereas, in Example 9 1.5 P t n molecular equivalents of chlorosulfonic acid was 816811 ll T011911 1 used. We have discovei ed that some members 01 Exam 1e Percent M. P.,

N Glummmlde Yield 0., the series of new compounds of our invention, Found Theory particularly those in which the R represents a radical of more than 8 carbon atoms, which congg g z i; 3;; tain only one sulfate group per molecule, are not dodegyl..l 35.5 -1g: g2 2.2 completely soluble in water in 1 percent concentetra ec octadeculfiienyl 86 145446 tration. Accoi dmg to our process, the degree of rosin 89 141-142 3.0 2. 7 sulfation may be varied to increase the molecular ratio up to 3:1 and higher. This may be accomplished simply by employing the requisite proportion of sulfating agent. A series of experiments The sulfated D-gluconamides of this invention was performed in which R radicals and molecular and the corresponding sodium salts were preratios were varied. The results are summarized pared as illustrated in the following examples. in Table II.

PercengnNitro' Percent Sulfur Mole Example Gluconamide Percent g SOaNa No. Sulfate Yield per Found Theory Found Theory Molecule EXAMPLE 8 Preparation of sodium. N-Z-ethylheryZ-D-gluconamide sulfate A suspension was prepared consisting of 18.4 g. of N-2-ethylhexyl-D-gluconamide in 200 ml. of dry methylene chloride. To this suspension was added portion-wise a solution of 7.0 g. of chlorosulfonic acid dissolved in 20 ml. of methylene chloride. During the addition, the reaction mixture was stirred and maintained under' gentle reflux. Stirring and refluxing was continued for 4 hours after the addition was completed. Methylene chloride and hydrogen chloride were removed from the reaction mixture by a stream of dry air, leaving a white residue of N-2-ethylhexyl-D-gluconamide sulfuric ester. This was dissolved in 50 percent ethanol and. neutralized to pH 7.1 with sodium hydroxide solution. The neutral solution was concentrated in vacuo to dryness. The residue was extracted withacetone and the residual dry white salt weighed 23.1 .g., a yield of 94' percent of theory.

Analysia-Calcd. for: C1-4I-I2sO9SNNa: N, 3.4. Found: N, 3.3.

EXAMPLE 9 Preparation of sodium N-dodecyZ-D- gluconamide sulfate The procedure of Example 8 was followed in reacting 25.4 g. of N-dodecyl-D-gluconamide with 12.2 g. of chlorosulfonic acid. N-dodecyl-D- The above examples are not to be construed as as limitative. Calcium, magnesium, iron, chromium, aluminum, nickel, ammonium, and substituted ammonium salts, and pyridinium, quinclinium, and others are prepared from the sulfuric acid by precipitation with the corresponding base, or from the sodium compound by metathesis with the corresponding salt of the metal, ammonia, or amine. Other cycloaliphatic, hydroaromatic, and cycloaliphatic substituted alkyl amines are obviously substitutable for the amines listed above, such as c-alkyl substituted cyclopentadienyl amines and cyclopentylamines, and cyclohexylalkylamines, alkyl-cyclohexenylamine, cyclohexenylallsylamines, and cyclohexadienylamines. Amines having more than 18, for example, up to about 32 or more carbon atoms are also within the scope of this disclosure.

Having thus described our invention, we claim:

1. A gluconamide compound of the formula:

RNHCO (CHOI-I) 403201-11 in which R is a hydrocarbon radical taken from the group consisting of alkyl radicals having from 8 to 18 carbon atoms and resin radicals, and in which at least one hydroxyl group of the gluconyl radical is replaced by the radical $04M in which M is taken from the group consisting of hydrogen and alkali metals.

2. Sodium N-2-ethylhexyl-D-gluconamide sulfate.

3. sodium N-dodecyl-D-gluconamide sulfate.

4. Sodium N-rosin-D-gluconamide sulfate.

5. A compound of the formula RNHCO (CHOH) 4CH2OSO3M in which M is a cation and R is an aliphatic hystraight and open chain of at least six carbon 5 drocarbon radical having at least 8 carbon atoms. by the radical -.SO4M in which M is an alkali 6. A gluconamide compound of the formula: metal radical.

I CHARLES L. MEHLTRETTER. RNHC0 CHOH 4CH2OH RUSSELL L. MELLIES. in which RNI-I is the radical of a rosin amine, and 5 JOHN RANKIN- in which at least one hydroxyl group of the gluconyl radical is replaced by the radical References Cited m the file of this patent -SO4M in which M is an alkali metal radical. UN STATES PATENTS '7. A gluconamide compound of the formula: Number Name Date 2,216,617 Katz Oct. 1, 1940 RNHCWCHOHMCEOH 2,267,609 Kern Dec. 23, 1941 in which formula R is an alkyl radical having not OTHER REFERENCES less than eight carbon atoms and having a Goldner et al., J. Am. Pharm. Assoc., vol. 2

atoms, and n which formula at least one h 1 y J. A. c. s.. vol. 66, pp. 1516-1520 (1944).

droxyl group of the gluconyl radical is replaced 

1. A GLUCONAMIDE COMPOUND OF THE FORMULA:
 4. SODIUM N-ROSIN-D-GLUCONAMIDE SULFATE. 